Full metadata record
DC Field | Value | Language |
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dc.contributor.author | 남원우 | * |
dc.date.accessioned | 2022-02-22T16:31:15Z | - |
dc.date.available | 2022-02-22T16:31:15Z | - |
dc.date.issued | 2021 | * |
dc.identifier.issn | 0947-6539 | * |
dc.identifier.issn | 1521-3765 | * |
dc.identifier.other | OAK-30678 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/260665 | - |
dc.description.abstract | High-valent iron-imido complexes can perform C-H activation and sulfimidation reactions, but are far less studied than the more ubiquitous iron-oxo species. As case studies, we have looked at a recently published iron(V)-imido ligand pi-cation radical complex, which is formally an iron(VI)-imido complex [Fe-V(NTs)(TAML(+.))] (1; NTs=tosylimido), and an iron(V)-imido complex [Fe-V(NTs)(TAML)](-) (2). Using a theoretical approach, we found that they have multiple energetically close-lying electromers, sometimes even without changing spin states, reminiscent of the so-called Compound I in Cytochrome P450. When studying their reactivity theoretically, it is indeed found that their electronic structures may change to perform efficient oxidations, emulating the multi-spin state reactivity in (FeO)-O-IV systems. This is actually in contrast to the known [Fe-V(O)(TAML)](-) species (3), where the reactions occur only on the ground spin state. We also looked into the whole reaction pathway for the C-H bond activation of 1,4-cyclohexadiene by these intermediates to reproduce the experimentally observed products, including steps that usually attract no interest (neither theoretically nor experimentally) due to their non-rate-limiting status and fast reactivity. A new "clustering non-rebound mechanism" is presented for this C-H activation reaction. | * |
dc.language | English | * |
dc.publisher | WILEY-V C H VERLAG GMBH | * |
dc.subject | C-H bond activation | * |
dc.subject | DFT | * |
dc.subject | nitrene transfer | * |
dc.subject | oxygen atom transfer | * |
dc.subject | reaction mechanism | * |
dc.title | Nonheme Iron Imido Complexes Bearing a Non-Innocent Ligand: A Synthetic Chameleon Species in Oxidation Reactions | * |
dc.type | Article | * |
dc.relation.issue | 69 | * |
dc.relation.volume | 27 | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 17495 | * |
dc.relation.lastpage | 17503 | * |
dc.relation.journaltitle | CHEMISTRY-A EUROPEAN JOURNAL | * |
dc.identifier.doi | 10.1002/chem.202103295 | * |
dc.identifier.wosid | WOS:000710758600001 | * |
dc.identifier.scopusid | 2-s2.0-85117786789 | * |
dc.author.google | Li, Xiao-Xi | * |
dc.author.google | Lu, Xiaoyan | * |
dc.author.google | Park, Jae Woo | * |
dc.author.google | Cho, Kyung-Bin | * |
dc.author.google | Nam, Wonwoo | * |
dc.contributor.scopusid | 남원우(7006569723) | * |
dc.date.modifydate | 20240116111857 | * |